Use of polymeric quaternary ammonium hydroxides in electrodeposition

ABSTRACT

Quaternary ammonium hydroxide-containing polymers and their use in cationic electrodeposition are disclosed. The quaternary ammonium hydroxide-containing polymers are particularly useful as feed resins for controlling the pH of aqueous dispersions of acidified cationic resins used in electrodeposition. Upon electrodeposition, such resins generate acid which can build up to undesirable levels in the electrodeposition bath. The quaternary ammonium hydroxide-containing polymers are strong bases and when fed into the bath react with the acid to form the corresponding quaternary ammonium salt. This controls the pH of the bath at acceptable levels and provides additional cationic resin for electrodeposition. Utilizing the invention in this manner minimizes the need for controlling acid build-up in the electrodeposition bath by conventional techniques such as by treating the bath with ultrafiltration or electrodialysis. 
     The quaternary ammonium hydroxide-containing polymers are also useful as electrodeposition resins themselves in that they electrodeposit without generating acid counter ion.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to quaternary ammonium hydroxide-containing polymers and to their use in cationic electrodeposition. More particularly, this invention relates to the use of quaternary ammonium hydroxide-containing polymers in controlling the acid content of an aqueous electrodeposition bath which contains an acidified cationic resinous coating vehicle. The invention also relates to the use of quaternary ammonium hydroxide-containing polymers as coating vehicles for cationic electrodeposition.

2. Brief Description of the Prior Art

Cationic electrodeposition as practices on an industrial scale involves immersing a metallic article in an aqueous dispersion of a polymeric material which contains cationic groups such as quaternary ammonium salt groups or amine salt groups. An electric current is passed through the dispersion between the metallic article as cathode and a counter electrode as anode to cause a deposition of the coating on the cathode. During the electrodeposition, acid is generated at the counter electrode and continuously builds up in the bath where it can corrode equipment and raise the conductivity of the bath making it more difficult to electrodeposit smooth uniform coatings.

The art has recommended numerous ways to control this acid build-up such as by subjecting the bath to ultrafiltration and electrodialysis. However, these methods have shortcomings associated with them in that they require additional equipment costs as well as the expense of monitoring and maintaining the additional equipment.

The present invention overcomes many of the disadvantages of the prior art. In the present invention, the acid build-up is controlled by adding a quaternary ammonium hydroxide-containing polymer to the electrodeposition bath. The quaternary ammonium hydroxides are strong bases and react with the acid to form the corresponding quaternary ammonium salt of the acid. Thus, fresh resinous vehicle is provided and the pH of the bath is controlled and maintained at acceptable levels with no additional equipment costs.

SUMMARY OF THE INVENTION

In the present invention, a quaternary ammonium hydroxide-containing resin is formed, for example, by reacting a polyglycidyl ether of a polyphenol with an amine, preferably a tertiary amine, in the presence of water. The preferred resins are prepared by reacting a polyglycidyl ether of a polyphenol with an amine, preferably a tertiary amine in the presence of water.

The quaternary ammonium hydroxide-containing resins can be used as feed resins for an electrodeposition bath containing an acidified (e.g., lactic or acetic acid) electrocoating resin such as a quaternary ammonium salt group-containing resin or an amine salt group-containing resin. When these acid-solubilized resins electrodeposit, they generate acid at the anode(e.g., lactic or acetic acid) which does not coat out and builds up in the electrodeposition bath if not removed. The quaternary ammonium hydroxide-containing resins can be fed into the bath where they will neutralize the acid forming the corresponding quaternary ammonium salt of the acid. This controls the pH of the bath, maintains it at acceptable levels and provides additional cationic resin for electrodeposition.

The quaternary ammonium hydroxide-containing polymers can also be used as the sole charged electrocoating vehicle. When the polymers are dispersed in water and an electric current passed between an electroconductive cathode and an anode, in electrical contact with a polymeric dispersion, the polymer deposits on the cathode without generating harmful counter ion at the anode.

PERTINENT PRIOR ART

U.S. Pat. No. 3,839,252 to Bosso and Wismer discloses quaternary ammonium salt group-containing resins, useful for electrodeposition, which are prepared by reacting organic polyepoxides with amine acid salts in the presence of water. The reference does not disclose polymeric quaternary ammonium hydroxides nor the use of polymeric quaternary ammonium hydroxides in electrodeposition baths, such as provided in the instant invention.

U.S. Pat. No. 2,676,166 to Webers discloses quaternary ammonium salt group and quaternary ammonium hydroxide-containing polymers prepared by reacting epoxy-containing acrylic polymers with tertiary amines in the presence of acid and/or water. The polymer quaternary ammonium hydroxides are disclosed as being neutralizable with acid. The reference does not disclose that the quaternary ammonium hydroxides would be useful in electrodeposition such as provided in the instant invention.

DETAILED DESCRIPTION

The quaternary ammonium hydroxide-containing polymers can be formed by reacting an epoxy-containing polymeric material with an amine, preferably a tertiary amine, in the presence of water.

The epoxy-containing polymer is a resinous polyepoxide, that is, a polymeric resinous material containing two or more epoxy groups per molecule. The preferred polyepoxides are polyepoxides and polyglycidyl ethers of polyphenols such as Bisphenol A. These can be produced, for example, by etherification of a polyphenol with epihalohydrin or dihalohydrin such as epichlorohydrin or dichlorohydrin in the presence of alkali. The polyphenol can be, for example, bis-2,2-(4-hydroxyphenyl)propane, 4,4'-dihydroxybenzophenone, bis-1,1-(4-hydroxyphenyl)ethane, bis-1,1-(4-hydroxyphenyl)isobutane, bis-2,2-(4-hydroxytertiarybutyl-phenyl)propane, bis-(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene or the like.

While the polyglycidyl ethers of the polyphenols may be employed per se, it is frequently desirable to react a portion of the reactive sites (i.e., hydroxy) with a modifying material to vary the film characteristics of the polymer. The esterification of the epoxy-containing polymers with carboxylic acids, especially fatty acids, is well known in the art and need not be discussed in detail. Especially preferred are saturated fatty acids, and especially pelargonic acid. Likewise, the epoxy resin may be modified with isocyanate group-containing organic materials such as half-capped diisocyanates such as disclosed in U.S. Pat. No. 3,922,253 to Jerabek and Marchetti.

Another quite useful class of polyepoxides is produced from Novolak resins or similar polyphenol resins.

Also suitable are similar polyglycidyl ethers of polyhydric alcohols which may be derived from such polyhydric alcohols as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol, bis-2,2-(4-hydroxycyclohexyl)-propane and the like.

There can also be used polyglycidyl esters of polycarboxylic acids which are produced by the reaction of epichlorohydrin or a similar epoxy compound with an aliphatic or aromatic polycarboxylic acid such as succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, dimerized linolenic acid and the like. Examples are poly(glycidyl adipate) and poly(glycidyl phthalate).

The preferred epoxy-containing polymeric materials are polyglycidyl ethers of polyphenols, particularly Bisphenol A. The products are preferably further reacted to chain extend and increase their molecular weight. For example, they may be further reacted with active hydrogen-containing materials, which are reactive with epoxy groups, such as those containing --OH, --SH, --COOH, ═NH groups. Preferred chain extenders are organic polyols. Chain extending of epoxy-containing polymeric materials with organic polyols including polymeric polyols is disclosed in U.S. Pat. application Ser. No. 648,982 to Marchetti, Zwack and Jerabek, on page 6, line 8, continuing through to page 11, line 7.

Besides the polyglycidyl ethers mentioned above, other epoxy-containing polymers which may be employed are acrylic polymers which contain epoxy groups. These polymers are formed by polymerizing an unsaturated epoxy-containing monomer such as glycidyl acrylate or methacrylate by itself or with one or more other polymerizable ethylenically unsaturated monomers.

Examples of other polymerizable ethylenically unsaturated epoxy-containing monomers are allyl glycidyl ether, 4-vinylcyclohexene monoepoxide, butadiene monoepoxide, vinyl glycidyl phthalate, allyl glycidyl maleate, allyl glycidyl phthalate and the like.

Examples of other olymerizable ethylenically unsaturated monomers are those having at least one CH₂ ═CH< group. Examples of such monomers include vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, vinyl chloride, vinyl fluoride, isopropenyl acetate, vinylidene chloride, methyl vinyl ether, acrolein, methyl vinyl ketone, hydroxyethyl acrylate or methacrylate and hydroxypropyl acrylate or methacrylate.

The epoxy-containing acrylic polymers are prepared by techniques well known in the art. The acrylic monomers are usually polymerized either in bulk or in solvent using a free radical producing catalyst such as a peroxide-type catalyst or an azo compound. Examples of suitable catalysts are tertiary butyl peroxide and 2,2'-azobisisobutyronitrile. Usually, to control molecular weight, a chain transfer agent such as tertiary dodecyl mercaptan is also employed.

The amine which is reacted with the epoxy-containing polymers as described above may be selected from a wide variety of tertiary amines. Tertiary amines which may be used may be unsubstituted or substituted with substituents such as hydroxyl as long as the substituent does not interfere with the reaction of the amine with the epoxy-containing polymer, and the substituents are of such a nature or employed under conditions that they will not gel the reaction mixture. Examples of suitable tertiary amines include dimethylethanolamine, triethylamine, trimethylamine, triisopropylamine, and the like. Examples of other tertiary amines are disclosed in U.S. Pat. No. 3,829,252 to Bosso and Wismer in column 5, line 3, through column 7, line 42.

The amine and the epoxy-containing polymer are reacted in the presence of water. If the quaternization reaction is carried out in the presence of water and in the absence of acids, quaternary ammonium hydroxides are produced. The amount of water is not critical but it is preferred that, based on amine groups, a stoichiometric equivalent or excess of water be used. Excess water can be used to control the exothermic amine-epoxy reaction. Thus, gelation may be avoided. Typically, the mole ratio of water to amine nitrogen is controlled between about 1.0 to about 16 moles of water per equivalent of amine nitrogen. Greater amounts of water are not recommended because they result in extremely slow or even non-reaction.

The reaction temperature may be varied between the lowest temperature at which reaction reasonably proceeds, for example, room temperature, or in the usual case, slightly above room temperature to a maximum temperature of about 100° C. (at atmospheric pressure). At greater than atmospheric pressure, higher reaction temperatures can be used. Usually, reaction temperatures range between about 60° to 100° C.

In the formation of the quaternary ammonium hydroxides, it is preferred that a stoichiometric excess of amine to epoxy be present during the reaction to avoid gelation. Thus, it is desirable to add the epoxy-containing polymer slowly to a mixture of amine and water in order to maintain an excess of amine. It is also desirable to carry out the reaction between the amine and epoxy at a fast rate. Slow reaction rates can lead to gelation.

With regard to the amount of tertiary amine and epoxy-containing polymer which are reacted with one another, the relative amounts can be varied and depend on the extent of quaternization desired, and this in turn will depend on the molecular weight and structure of the epoxy-containing polymer. The extent of quaternization, the molecular weight and structure of the epoxy-containing polymer should be selected such that when the quaternary ammonium hydroxide-containing polymer is mixed with an aqueous medium to form an electrodeposition bath, a stable dispersion will form. A stable dispersion is one which does not sediment or is one which is easily redispersed if some sedimentation occurs. In addition, the dispersion should be of sufficient cationic character that the dispersed resin particles will migrate towards the cathode when an electrical potential is impressed between an anode and a cathode immersed in the aqueous dispersion. Also, the molecular weight, structure and extent of quaternary ammonium hydroxide formation should be controlled so that the dispersed resin will have the required flow to form a film on a cathode. The film must be insensitive to moisture to the extent that it will not redissolve in the electrodeposition bath or be rinsed away from the coated cathode after its removal from the bath.

The structure, molecular weight and degree of quaternization are dependent on one another and the selection of one can only be made after a consideration of the other two. For example, because of flow considerations, the quaternary ammonium hydroxide-containing polymers prepared from polyglycidyl ethers of polyphenols should be of lower molecular weight than many of the epoxy-containing acrylic polymers mentioned above. In addition, higher molecular weight polymers usually require higher quaternary ammonium hydroxide contents than lower molecular weight polymers, unless the polymers contain hydrophilic groups such as poly(oxyalkylene) moieties.

In general, however, most of the quaternary ammonium hydroxide-containing polymers useful in the practice of the present invention have molecular weights within the range of 500 to 60,000 and contain from about 0.01 to 10 milliequivalents of quaternary nitrogen base group per gram of resin solids. Obviously, one must use the skill of the art to couple the molecular weight with the quaternary nitrogen base group content to arrive at a satisfactory polymer. With regard to the quaternary ammonium hydroxide-containing polymers prepared from the preferred polyglycidyl ethers of polyphenols, the molecular weight of the preferred polymers fall within the range of 500 to 10,000, more preferably 1,000 to 5,000. These preferred polymers will contain from 0.01 to 8.0, preferably 0.05 to 6.0 milliequivalents of quaternary nitrogen base group per gram of polymer.

When it is desired that the quaternary ammonium hydroxide-containing resins contain free epoxy groups, the ratio of starting organic epoxy-containing polymer to tertiary amine is selected so as to provide an excess of epoxy groups, thereby producing a resin containing free unreacted epoxy groups. Epoxy-free resins can be prepared by reacting the stoichiometric amounts of tertiary amine with the available epoxy groups. Epoxy-free resins can also be provided by preparing epoxy-containing reaction products and post-reacting the epoxy groups with active hydrogen-containing materials such as fatty acid, phenols and mercaptans.

Besides the tertiary amines described above, useful resins of the invention can be prepared with primary and secondary amines. This is accomplished by first reacting the primary or secondary amine with an epoxy-containing polymer and heating the reaction mixture to a suitable reaction temperature. The amine and the epoxy groups which may be from the resinous polyepoxide or from externally added epoxy such as propylene oxide, are reacted until a tertiary amine is formed. Further reaction causes tertiary amine to react with any residual remaining epoxy groups present to form the quaternary ammonium base group. When using primary or secondary amines, some precautions should be taken to avoid gelling of the resin. When quaternization is effected through the polymeric epoxy moiety, the molecular weight should be low and/or the epoxy equivalent weight high to avoid gelling. If higher molecular weight and/or lower epoxy equivalent weights are needed for good electrocoating properties, the quaternization should be effected with externally added epoxy.

The quaternary ammonium hydroxide-containing polymers can be used as the sole cationic electrocoating vehicle themselves, or, preferably, they can be used in combination with acid-solubilized cationic electrocoating resins.

Use of the quaternary ammonium hydroxide-containing polymers as the sole electrocoating vehicles is desirable because the polymers electrodeposit on the cathode without generating acid from the counter ion which will build up in the bath.

The preferred use of the quaternary ammonium hydroxide-containing polymers is in combination with acid-solubilized cationic resins. When the acid-solubilized cationic resins electrodeposit, they generate acid which does not coat out and builds up in the electrodeposition bath if not removed. Quaternary ammonium hydroxide-containing polymers can be added to the electrodeposition bath where they will neutralize the acid and form the corresponding quaternary ammonium salt group-containing polymer which will electrodeposit on the cathode.

Examples of acidified cationic electrodeposition resins are amine acid salt-containing polymers and quaternary ammonium salt group-containing polymers which are acidified with a relatively strong acid, that is, an acid having a dissociation constant greater than 1 × 10⁻⁵.

Examples of amine acid salt-containing polymers are those prepared by reacting an organic epoxy-containing polymer such as described above with a secondary amine in the presence of an organic solvent to form the tertiary amine. The amine-containing adducts can then be acidified to form the salt. Such resins are described in U.S. Pat. No. 3,984,299 to Jerabek; U.S. Pat. No. 3,947,338 to Jerabek and Marchetti and U.S. Pat. No. 3,947,339 to Jerabek, Marchetti and Zwack.

Examples of quaternary ammonium salt group-containing polymers are those prepared by reacting an epoxy-containing polymer such as those described above with a tertiary amine acid salt in the presence of water. These polymers are described in U.S. Pat. No. 3,839,252 to Bosso and Wismer.

The preferred use of the quaternary ammonium hydroxide-containing polymers is as a feed resin to an electrodeposition bath which contains an acid-solubilized resinous vehicle, such as those mentioned above. When fed into an electrodeposition bath employing these particular resinous vehicles, the quaternary ammonium hydroxide-containing resin will control the pH of the electrodeposition bath by neutralizing the acid that is generated during the electrodeposition process and will also act as a replenishment resin. When used as a feed or replenishment resin, the quaternary ammonium hydroxide-containing polymer is preferably of the same structure and molecular weight as the acid-solubilized resin originally used in the bath with the obvious exception that the feed resin contains hydroxide counter ion as opposed to acid counter ion.

When the quaternary ammonium hydroxide-containing resin is used as the sole feed or replenishment resin, some additional acid may also be added to the bath or the quaternary ammonium hydroxide-containing resin can be partially neutralized with acid before adding the resin to the bath to compensate for the acid removed from the bath by evaporation and drag-out.

Besides being used as the sole replenishment resin, the quaternary ammonium hydroxide-containing resin can be used as a partial replacement resin along with other acid-solubilized resinous electrocoating vehicles which may have the same or different structures and molecular weights.

The quaternary ammonium hydroxide-containing resin can be fed into the electrodeposition bath in a manner well known in the art. It is important that upon addition the quaternary ammonium hydroxide-containing resin does not cause instability in the electrodeposition bath. For example, the quaternary ammonium hydroxide-containing resin can be pre-mixed with paint withdrawn from the bath and the mixture added. Addition can be either on a continuous or incremental basis as is well known in the art.

The electrodeposition baths used in the practice of the invention have the resinous coating vehicles in the form of an aqueous dispersion. The term "dispersion" as used within the context of the present invention is believed to be a two-phase, transparent, translucent or opaque aqueous resinous system in which the resin is in the dispersed phase and the water in the continuous phase. The average particle size diameter of the resinous phase is generally less than 10, preferably less than 5 microns.

The concentration of the resinous products in the aqueous medium depends upon the process parameters to be used and is, in general, not critical, but ordinarily, the major portion of the aqueous dispersion is water. For example, aqueous dispersions preferably contain from 1 to 50 percent by weight resin solids.

Besides water, the aqueous medium may contain a coalescing solvent. The use of a coalescing solvent may be, in some instances, for improved deposited film appearance. These solvents include hydrocarbons, alcohols, esters, ethers and ketones. The preferred coalescing solvents include monoalcohols, glycols and polyols as well as ketones and other alcohols. Specific coalescing solvents include isopropanol, butanol, isophorone, 4-methoxymethyl-2-pentanone, ethylene and propylene glycol, the monoethyl, monobutyl and monohexyl ethers of ethylene glycol and 2-ethylhexanol. The amount of coalescing solvent is not unduly critical and is generally between about 0.01 and 40 percent by weight, preferably, about 0.5 to about 25 percent by weight based on total weight of aqueous medium.

In most instances, a pigment composition and, if desired, various additives such as surfactants or wetting agents are included in the dispersion. The pigment compositions may be any of the conventional type comprising, for example, iron oxides, lead oxides, strontium chromate, carbon black, coal dust, titanium dioxide, talc, barium sulfate, as well as color pigments such as cadmium yellow, cadmium red, chromium yellow and the like. The pigment content of the dispersion is usually expressed as the pigment-to-resin ratio. In the practice of the present invention, pigment-to-resin ratios within the range of 0.01 to 5:1 are usually used. The other additives mentioned above are present in the dispersion in amounts of 0.01 to 3 percent by weight based on total weight of resin solids.

The aqueous dispersion can also contain the curing agent for the electrocoating vehicle. Many of the electrocoating vehicles employed in the practice of the invention will contain active hydrogens such as hydroxyl and/or amine groups. In these instances, the curing agents should be those which are reactive with the active hydrogens. Examples include blocked isocyanates, phenolic resins and amine-aldehyde resins. Examples of some of these curing agents in cationic electrodeposition are found in U.S. Pat. No. 3,984,299 to Jerabek; U.S. Pat. No. 3,947,338 to Jerabek and Marchetti and U.S. Pat. No. 3,937,679 to Bosso and Wismer.

In the electrodeposition process employing the aqueous dispersions described above, the aqueous dispersion is placed in contact with an electrically conductive anode and an electrically conductive cathode with the surface to be coated being the cathode. While in contact with the aqueous dispersion, an adherent film of the coating composition is deposited on the cathode when a voltage is impressed between the electrodes.

The conditions under which electrodeposition is carried out are, in general, similar to those used in electrodeposition of other types of coatings. The applied voltage may be varied and can be, for example, as low as one volt or as high as several thousand volts, but typically between 50 and 500 volts. The current density is usually between 1.0 ampere and 15 amperes per square foot and tends to decrease during electrodeposition indicating the formation of a self-insulating film.

The method of the invention is applicable to coatings with any electrically substrate, especially metal such as steel, aluminum, copper magnesium and the like but also including metallized plastic and conductive carbon coated material. After electrodeposition, the coating is cured, usually by baking at elevated temperatures, temperatures of from about 90° to 260° C. for about 1 to 30 minutes are typical.

Illustrating the invention are the following examples, which, however, are not to be construed as limiting the invention to their details. All parts and percentages in the examples, as well as throughout this specification, are by weight unless otherwise indicated.

EXAMPLE I

The following example shows the preparation of a quaternary ammonium hydroxide-containing polymer from reacting a polyglycidyl ether of a polyphenol with a tertiary amine in the presence of water. The quaternary ammonium hydroxide-containing polymer was then used as a feed resin to control the pH of an electrodeposition bath which contained an acidified cationic resinous coating vehicle.

The acidified cationic resinous coating vehicle was an amine acid salt group-containing resin which was prepared by charging into a suitable reactor 970 parts by weight of EPON 1001 (polyglycidyl ether of Bisphenol A having an epoxy equivalent weight of 508 and commercially available from Shell Chemical Company) and 265 parts by weight of a polycaprolactonediol sold commercially by Union Carbide Corporation under the trade name PCP 0200. This particular product was believed to be made by the ring opening of epsilon-caprolactone with ethylene glycol to produce a polymer having a molecular weight of approximately 543. This charge was heated to 100° C. under a nitrogen blanket and 0.46 parts of benzyldimethylamine added. The reaction mixture was heated further to 130° C. where it was held for about 11/2 hours. The batch was then cooled to 110° C. and 110 parts by weight of methyl isobutyl ketone was introduced into the reaction vessel followed by 39.8 parts by weight of a 73 percent non-volatile solution of the ketoxime formed from reacting methyl isobutyl ketone and diethylene triamine in methyl isobutyl ketone solvent followed by an additional 100 parts by weight of methyl isobutyl ketone. Cooling was contined until the bath reached 70° C. at which point 53.1 parts by weight of diethylamine were introduced and the batch reheated to 120° C. where it was held for 3 hours and then discharged.

576 parts of the above-described polycaprolactonediol chain extended polyepoxide was blended with 310 parts by weight of a polyurethane crosslinker and 13.2 parts of dibutyltin dilaurate catalyst followed by neutralization with 12.3 parts of glacial acetic acid and reduced with sufficient deionized water to form a 40 percent resin solids dispersion.

The polyurethane crosslinker was prepared by adding 218 parts by weight of 2-ethylhexanol slowly to 291 parts by weight of an 80/20 isomer mixture of 2,4-/2,6-toluene diisocyanate under agitation and a dry nitrogen blanket, keeping the reaction temperature under 100° F. (38° C.) by external cooling. The charge was held an additional 1/2 hour at 100° F. (38° C.) and then heated to 140° F. (60° C.) at which point 75 parts by weight of trimethylolpropane were added followed by 0.08 parts of dibutyltin dilaurate catalyst. After an initial exotherm, the batch was held at 250° F. (121° C.) for 11/2 hours until essentially all of the isocyanate moiety was consumed as indicated by an infrared scan. The batch was then thinned with 249 parts of ethylene glycol monoethyl ether.

A pigment grinding vehicle was prepared from the following charge:

    ______________________________________                                         Ingredient           Parts by Weight                                                                            Solids                                        ______________________________________                                         EPON 829             710.0       681.2                                         Bisphenol A          289.6       289.6                                         2-ethylhexanol half-capped toluene                                             diisocyanate in methyl isobutyl ketone                                                              406.4       386.1                                         quaternizing agent.sup.a                                                                            496.3       421.9                                         deionized water      71.2        --                                            butyl CELLOSOLVE     56.76       --                                            ______________________________________                                         .sup.a Quaternizing agent was an organic tertiary amine acid salt              prepared                                                                       from the following charge:                                                     Ingredient           Parts by Weight                                                                            Solids                                        ______________________________________                                         2-ethylhexanol half-capped                                                     toluene diisocyanate in methyl                                                 ethyl ketone         320.0       304                                           dimethylethanolamine 87.2        87.2                                          aqueous lactic acid solution                                                                        117.6       88.2                                          butyl CELLOSOLVE     39.2        --                                            ______________________________________                                    

The 2-ethylhexanol half-capped toluene diisocyanate was added to the dimethylethanolamine in a suitable reaction vessel at room temperature. The mixture exothermed and was stirred for one hour at 80° C. Lactic acid was then charged followed by the addition of butyl CELLOSOLVE. The reaction mixture was stirred for about one hour at 65° C. to form the desired quaternizing agent.

To prepare the pigment grinding vehicle, the EPON 829 and Bisphenol A were charged under a nitrogen atmosphere to a suitable reaction vessel and heated at 150°-160° C. to initiate an exotherm. The reaction mixture was permitted to exotherm for one hour followed by cooling to 120° C. and the addition of the 2-ethylhexanol half-capped toluene diisocyanate added. The temperature of the reaction mixture was held at 110°-120° C. for one hour, followed by the addition of the butyl CELLOSOLVE. The reaction mixture was then cooled to 85°-90° C., homogenized and charged with water, followed by the addition of the quaternizing agent. The temperature of the reaction mixture was held at 85° C. until an acid value of one was obtained.

A pigment paste was prepared as follows:

    ______________________________________                                         Ingredient             Parts by Weight                                         ______________________________________                                         pigment grinding vehicle prepared as                                           described above        240.55                                                  deionized water        478.75                                                  ASP-17 clay            240.55                                                  lead silicate          42.24                                                   carbon black           33.68                                                   ______________________________________                                    

The ingredients were mixed in a Cowles mixer for about 10 minutes and the mixture combined with 22.12 parts by weight of strontium chromate and ground in a Zircoa mill to a Hegman No. 7 grind.

A catalyst, dibutyltin oxide, in the form of a pigment paste was prepared from the following charge:

    ______________________________________                                         Ingredient             Parts by Weight                                         ______________________________________                                         pigment grinding vehicle prepared as                                           described above        201.54                                                  deionized water        460.35                                                  dibutyltin oxide       283.67                                                  ______________________________________                                    

The above charge was ground in a Zircoa mill to a Hegman No. 7 grind.

An electrodeposition bath was prepared by mixing the following ingredients in 1835 parts by weight of deionized water:

    ______________________________________                                         Ingredient             Parts by Weight                                         ______________________________________                                         acetic acid            2.5                                                     amine acid salt-containing resin prepared                                      as described above     1590                                                    pigment paste          357                                                     catalyst paste         15.5                                                    ______________________________________                                    

100 parts by weight of a 10 percent by weight acetic acid aqueous solution was added to the electrodeposition bath prepared as described above to simulate build-up of acid which occurs in an electrodeposition bath after it has been in use for a period of time. The pH of the electrodeposition bath dropped from 6.25 to 5.3. 216 parts by weight of the quaternary ammonium hydroxide-containing resin prepared as described below was added to the bath and raised the pH to 6.0 evidencing neutralization of the acid and formation of the quaternary ammonium salt. Zinc phosphated steel panels were cathodically electrodeposited with this electrodeposition bath at 270 volts for 2 minutes at a bath temperature of 80° F. (27° C.) to give a textured 0.5 mil film. Both the tertiary amine acid salt-containing resin and the quaternary ammonium base group resin electrodeposited. The electrodeposition bath evidenced a 2 minute Ford throwpower of 9 1/8 inches at 270 volts at a bath temperature of 82° F. (28° C.).

The quaternary ammonium hydroxide-containing polymer was prepared from the following charge:

    ______________________________________                                         Ingredient             Parts by Weight                                         ______________________________________                                         EPON 829.sup.1         219.7                                                   Bisphenol A            89.4                                                    toluene diisocyanate half-capped with                                          2-ethylhexanol         125.7                                                   butyl CELLOSOLVE.sup.2 194.9                                                   butyl CELLOSOLVE       194.9                                                   deionized water        60                                                      adduct of 2-ethylhexanol half-capped toluene                                   diisocyanate and dimethylethanolamine                                                                 158.3                                                   ______________________________________                                          .sup.1 EPON 829 is an epoxy resin solution made from reacting                  epichlorohydrin and Bisphenol A having an epoxy equivalent of 193-202 and      commercially available from Shell Chemical Company.                            .sup.2 Ethylene glycol monobutyl ether.                                  

The EPON 829 and Bisphenol A were charged to a reaction vessel and heated to exotherm for about one hour and 18 minutes, the highest temperature reaching 190° C. The reaction mixture was cooled to 120° C. and the adduct of one mole of 2-ethylhexanol and one mole of toluene dissocyanate was added. The reaction mixture was held at 120° C. for 1 hour followed by the addition of the first portion of butyl CELLOSOLVE and then cooling to 85° C. The second portion of butyl CELLOSOLVE, deionized water and the adduct of one mole of dimethylethanolamine, one mole of toluene diisocyanate and one mole of 2-ethylhexanol was added and the reaction mixture held at 75° C. for 1 hour followed by cooling to room temperature. The reaction mixture had a solids content of 56.64 percent, a Gardner-Holdt viscosity of Z₃ ⁻ and contained 0.58 milliequivalents of total base per gram of resin solids and 0.453 milliequivalents of quaternary ammonium base groups per gram of solids indicating 78.2 percent of the total base groups were quaternary ammonium hydroxide groups.

EXAMPLE II

The following example shows the preparation of a quaternary ammonium hydroxide-containing polymer from reacting a polyglycidyl ether of a polyphenol with a tertiary amine in the presence of water. The quaternary ammonium hydroxide-containing polymer was then used as an electrocoating vehicle and as feed resin to control the pH of an electrodeposition bath which contajned an acidified cationic resinous coating vehicle.

The polyglycidyl ether of a polyphenol was prepared from the following charge:

    ______________________________________                                                            Parts by Weight                                             Ingredient           Solids    Grams                                           ______________________________________                                         EPON 829             600.0     625.0                                           Bisphenol A          202.0     202.0                                           PLURONIC L-31.sup.1  368.0     368.0                                           TEXANOL.sup.2        --        62.0                                            dimethylethanolamine 2.5       2.5                                             88% by weight aqueous lactic                                                                        2.6       3.0                                              acid solution                                                                 methyl ethyl ketone  --        304.3                                           ______________________________________                                          .sup.1 Polypropylene glycol terminated with ethylene glycol moieties           having a molecular weight of about 1200, commercially available from BASF      Wyandotte Company.                                                             .sup.2 2,2,4-trimethylpentane-1,3-diol monoisobutyrate.                  

The EPON 829 and the Bisphenol A were charged to a reaction vessel and heated over a period of about 35 minutes to exotherm at 150° C. The exotherm was maintained for about 25 minutes with the highest temperature being about 210° C. The reaction mixture was then cooled to room temperature and the PLURONIC L-31 and TEXANOL were added. The reaction mixture was then heated to 125° C. followed by the addition of the dimethylethanolamine (catalyst for chain extension of polyepoxide with PLURONIC L-31). The temperature was maintained at 125°-133° C. for about 2 hours and 35 minutes at which point in time the reaction mixture had a P Gardner-Holdt viscosity measured at 25° C. at 46.6 percent solids in ethyl CELLOSOLVE. The lactic acid was then added to neutralize the dimethylethanolamine catalyst followed by thinning of the reaction mixture with methyl ethyl ketone. The reaction mixture was then cooled to room temperature.

1567 parts by weight of the epoxy resin reaction mixture prepared as described immediately above (1175 parts by weight solids) was added steadily to a 50 percent by weight aqueous solution of dimethylethanolamine to form the quaternary ammonium hydroxide. The addition was over the period of about 2 hours and the temperature was maintained at about 82°-84° C. At the completion of the addition, the reaction mixture was thinned with 74 parts by weight of phenyl CELLOSOLVE (ethylene glycol monophenyl ether) followed by distilling to remove the methyl ethyl ketone. The resin was very viscous and was thinned with 500 milliliters of deionized water, warmed to 85° C. and thinned again with 827.7 parts by weight of deionized water to form about a 47 percent by weight solids dispersion. The quaternary ammonium hydroxide-containing polymer contained 0.342 milliequivalents of quaternary ammonium base groups per gram of resin based on resin solids.

The aqueous dispersion of the quaternary ammonium hydroxide-containing polymer prepared as described above was thinned with additional deionized water to form a 10 percent solids electrodeposition bath. The bath had a pH of 11.0 and appeared to be greenish-brown in color. Zinc phosphated steel panels were electrocoated in this bath at a bath temperature of about 80° F. (27° C.) at 100 volts for approximately 45 seconds. The maximum amperage was 0.5 amps which dropped to 0.04 amps during deposition. A thicker than desired, somewhat porous film was electrodeposited on the side of the panels facing the anode. Most of the panel facing away from the anode was only partially coated. The deposited film was not sensitive to a deionized water rinse.

When 463 parts by weight of the 40 percent by weight aqueous dispersion of the quaternary ammonium hydroxide-containing resin prepared as described above was added to 3,500 parts by weight of the excess acid-containing electrodeposition bath described in Example I, the pH of the electrodeposition bath was raised from 5.4 to 6.0. Zinc phosphated steel panels were cathodically electrodeposited with this electrodeposition bath at 50 volts for 2 minutes at a bath temperature of 80° F. (27° C.) to give a 0.35 mil film build-up with both cationic resins in the bath being electrodeposited.

The 10 percent solids aqueous electrodeposition bath prepared as described above was modified with about 5 percent by weight (based on resin solids) of 2-ethylhexanol to improve the electrodeposited film appearance. A zinc phosphated steel panel was electrocoated in this bath at a bath temperature of about 80° F. (27° C.) at 125 volts for approximately 90 seconds. The maximum amperage was 0.8 amps which dropped to 0.13 amps during deposition. A relatively thin, clear, colorless, continuous film deposited on both sides of the panel. The coated panel was baked at 400° F. (204° C.) for 20 minutes to produce a dark yellow film which shows good solvent resistance, that is, the film softens but is not removed by rubbing with an acetone-saturated cloth.

EXAMPLE III

The following example shows the preparation of a quaternary ammonium hydroxide-containing polymer from reacting a polyglycidyl ether of a polyphenol with a tertiary amine in the presence of water. The quaternary ammonium hydroxide-containing polymer was then used as an electrocoating vehicle and as a feed resin to control the pH of an electrodeposition bath which contained an acidified cationic resinous coating vehicle.

The quaternary ammonium hydroxide-containing polymer was prepared from the following charge:

    ______________________________________                                         Ingredient         Parts by Weight                                             ______________________________________                                         EPON 1001          622.9                                                       PCP 0200           176.4                                                       xylene             49.4                                                        benzyldimethylamine catalyst                                                                      2.2                                                         dimethylcyclohexylamine                                                                           83.4                                                        deionized water    236.6                                                       butyl CELLOSOLVE   236.6                                                       ______________________________________                                    

The EPON 1001, PCP 0200 and xylene were charged to a reaction vessel and heated under a nitrogen blanket to 195° C. for about 30 minutes. The reaction mixture was cooled to 130° C. and the benzyldimethylamine catalyst added. Reaction was continued for about 2 hours at about 120°-130° C. The reaction mixture was cooled to about 113° C. followed by the addition of the dimethylcyclohexylamine, deionized water and butyl CELLOSOLVE (all of which were blended together). The reaction mixture was held for two hours at 75°-80° C. to effect quaternization. The reaction mixture was then cooled to room temperature. The quaternary ammonium hydroxide-containing polymer contained 0.748 milliequivalents of total base per gram of resin and 0.655 milliequivalents of quaternary ammonium base group per gram of resin based on resin solids.

The quaternary ammonium hydroxide-containing resin prepared as described above was thinned with 2-ethylhexanol and deionized water in proportions shown below to form a 10 percent solids electrodeposition bath.

    ______________________________________                                         Ingredient        Solids   Parts by Weight                                     ______________________________________                                         quaternary ammonium hydroxide-                                                 containing resin  108.0    282.6                                               2-ethylhexanol    --       9.5                                                 deionized water   --       1508.0                                              ______________________________________                                    

The quaternary ammonium hydroxide-containing resin was blended with the 2-ethylhexanol and then reduced with the deionized water with stirring. A uniform white dispersion was obtained having a pH of 9.8.

Iron phosphated cold rolled steel panels were electrodeposited in this bath at 300 volts for 90 seconds at a bath temperature of 77° F. (25° C.). The amperage cut off was sharp, dropping from 2.8 to 0.15 amps. A colorless uniform film was obtained. The film was baked at 300° F. (149° C.) for 20 minutes to give a colorless, glossy, smooth, hard film having a thickness of about 1.1 mil.

An acidified cationic resinous coating vehicle which was a quaternary ammonium lactate-containing resin was prepared from the following charge:

    ______________________________________                                         Ingredient       Parts by Weight                                                                              Solids                                          ______________________________________                                         EPON 829         1770          1708                                            Bisphenol A      302           302                                             propylene glycol (MW = 600)                                                                     850           850                                             dimethylethanolamine                                                                            6.5           6.5                                             lactic acid      7.5           6.6                                             2-ethylhexanol   51.8          --                                              FOAMKILL 639     12.2          12.2                                            isopropanol      129           --                                              dimethylethanolamine lactate                                                                    163.9         122.7                                           aqueous boric acid solution                                                                     167           7.5                                             deionized water  347           --                                              aqueous boric acid solution                                                                     300           13.5                                            CYMEL 1123.sup.1 300           300                                             isopropanol      248.5         --                                              ______________________________________                                          .sup.1 Benzoguanamine-formaldehyde condensate commercially available from      American Cyanamid Company.                                               

The EPON 829 and Bisphenol A were charged to a reaction vessel and heated to exotherm at 160° C. The exotherm was maintained for about 30 minutes followed by cooling to 100° C. and the addition of the polypropylene glycol and dimethylethanolamine. The reaction mixture was then heated to 130° C. and held at this temperature for about 51/2 hours, after which the 2-ethylhexanol, FOAMKILL 639, first portion of isopropanol, the dimethylethanolamine lactate, the first portion of boric acid and the deionized water were added. The reaction mixture was held at about 85° C. for about 1 hour followed by the addition of the second portion of boric acid. The benzoguanamine (curing agent) was then added followed by cooling of the reaction mixture to room temperature and thinning with the second portion of isopropanol.

The quaternary ammonium lactate-containing resin prepared as described above was thinned with deionized water to form an electrodeposition bath in the following charge ratio:

    ______________________________________                                         Ingredient        Parts by Weight                                                                              Solids                                         ______________________________________                                         quaternary ammonium lactate-                                                   containing resin   415.4        270.0                                          water             1384.6        --                                             ______________________________________                                    

The resin was reduced with the deionized water while stirring to give a white uniform dispersion having a pH of 6.0.

The above electrodeposition bath was acidified to a pH of 4.7 by adding 88 percent aqueous lactic acid to simulate build-up of acid which occurs in an electrodeposition bath after it has been in use for some time.

1000 parts by weight of the electrodeposition bath were removed and replaced with 1000 parts by weight of the quaternary ammonium hydroxide-containing electrodeposition bath prepared as described above in this example. The new bath had a pH of 6.2 An iron phosphated cold rolled steel panel was electrodeposited in this bath at 200 volts for 90 seconds, bath temperature 80° F. (27° C.). A colorless, continuous film was obtained. The film was baked at 400° F. (204° C.) for 20 minutes to give a colorless, smooth, glossy film having a thickness of about 0.9 mil. 

We claim:
 1. A method of forming a quaternary ammonium group-containing polymer and for controlling the pH of an aqueous electrodeposition bath which contains acid generated in the electrocoating process, the method comprising:1. forming a quaternary ammonium hydroxide-containing polymer,
 2. adding said quaternary ammonium hydroxide-containing polymer to the aqueous electrodeposition bath which contains an acidified cationic resinous coating vehicle and acid generated in the electrocoating process,
 3. neutralizing said acid with the quaternary ammonium hydroxide-containing polymer to form the corresponding quaternary ammonium salt group-containing polymer and to control the pH of the aqueous electrodeposition bath.
 2. The method of claim 1 in which the quaternary ammonium hydroxide-containing polymer is formed by reacting an epoxy-containing polymer with a tertiary amine in the presence of water.
 3. The method of claim 2 in which the epoxy-containing polymer is polyglycidyl ether of a polyphenol.
 4. The method of claim 1 in which the acidified cationic resinous coating vehicle is selected from the class consisting of amine acid salt and quaternary ammonium salt group-containing resins.
 5. A process for cathodically electrodepositing a coating on a conductive article which comprises the steps of:1. immersing the conductive article in an aqueous dispersion which contains an acidified cationic resinous coating vehicle,
 2. passing an electric current through the aqueous dispersion between the conductive article as cathode and another electrode as an anode to deposit the resinous coating vehicle on the cathode and to generate acid at the anode,
 3. feeding into said aqueous dispersion a polymeric quaternary ammonium hydroxide,
 4. reacting said hydroxide with said acid to form the corresponding quaternary ammonium salt of said acid.
 6. The method of claim 5 in which an acid is fed into said aqueous dispersion, said acid being sufficient to maintain the total amount of acid in the bath at an essentially constant level.
 7. The method of claim 5 in which the acidified cationic resinous coating vehicle is selected from the class consisting of amine acid salt and quaternary ammonium salt group-containing resins.
 8. The method of claim 5 in which the quaternary ammonium hydroxide is formed from reacting an epoxy-containing polymer with a tertiary amine in the presence of water. 